DBD plasma-assisted dry reforming of methane over Ni/SiO2
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摘要: 分别采用沉积沉淀法（DP）和浸渍法（IMP）制备Ni/SiO2催化剂前体，前体经H2还原得到Ni/SiO2-DP和Ni/SiO2-IMP。对所制备的催化剂进行X射线衍射、X射线光电子能谱、N2吸附-脱附、化学吸附、傅里叶变换红外、透射电镜和拉曼光谱表征，并考察其与介质阻挡放电等离子体（DBD）协同催化甲烷干重整（DRM）制合成气反应性能。研究结果表明，相较于Ni/SiO2-IMP，Ni/SiO2-DP因其较小的Ni颗粒尺寸、Ni与载体的强相互作用以及对反应物分子较强的吸附活化能力，具有更高的催化活性和稳定性。对Ni/SiO2-DP制备条件考察结果表明，H2等离子体还原（PR）的Ni/SiO2-DP-PR比程序升温还原（TPR）的Ni/SiO2-DP-TPR具有更高的催化活性。沉积沉淀时间为10 h，H2等离子体还原时间为30 min时，CH4和CO2转化率分别为72.5%和78.2%，H2和CO选择性分别为86.7%和94.2%，能量利用率为4.36 mmol/kJ。
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关键词:
- CH4/CO2重整 /
- Ni/SiO2 /
- 介质阻挡放电等离子体
Abstract: Dry reforming of methane reaction(DRM) utilizes both CH4 and CO2 greenhouse gases to convert them into synthesis gas (H2 and CO), which can be further synthesized into value-added chemicals such as hydrocarbons or liquid oxygen-containing compounds. The traditional thermal method for catalyzing DRM reaction often uses Ni-based catalysts. And it requires high reaction temperature (>700 ℃). The high temperature leads to sintering and carbon deposition of Ni-based catalysts, as well as low energy efficiency, which limits the application of this reaction. Dielectric barrier discharge plasma (DBD) can synergistically drive the reaction with Ni-based catalysts at low temperature, thereby addressing the drawbacks of thermal catalysis. The key of this technology is to develop catalysts that have synergistic effects with plasma and strong resistance to carbon deposition. Therefore, this paper uses nickel phyllosilicate as precursor and H2 plasma reduction to prepare highly dispersed Ni-based catalyst, which synergistically catalyze the DRM reaction with DBD plasma. Nickel phyllosilicate was prepared by deposition-precipitation method, and Ni/SiO2-DP was obtained after calcination and reduction. Ni/SiO2-IMP was prepared by impregnation method. The prepared catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, N2-adsorption-desorption, chemisorption, Fourier transform infrared, transmission electron microscope, thermogravimetric analysis and Raman spectra. The catalytic performance for dry reforming of methane (DRM) to synthesis gas was investigated in the dielectric barrier discharge(DBD) reactor. The research results indicate that Ni/SiO2 -DP has higher catalytic activity and stability, which benefits from its smaller Ni particles size, stronger interaction between Ni and support, and stronger adsorption ability for the reactants, compared with Ni/SiO2 -IMP. The CH4 and CO2 conversions of Ni/SiO2-DP are 61.7% and 70.0%. The selectivities of H2 and CO are 86.9% and 94.3%, and H2/CO is 0.92. The CH4 and CO2 conversions of Ni/SiO2-IMP are 44.2% and 28.4%. The selectivities of H2 and CO are 62.7% and 42.4%, and H2/CO is 1.48. After stability testing, the catalysts were characterized by TG. The weight loss of Ni/SiO2- IMP is 84.45%, while the weight loss of Ni/SiO2-DP is only 34.06%. The preparation conditions of Ni/SiO2 -DP were investigated. The results show that the Ni/SiO2-DP-PR from H2 plasma reduction(PR) exhibits higher catalytic activity than the Ni/SiO2-DP-TPR from temperature programmed reduction(TPR). DBD plasma reactor contains a large number of high energy particles, including H atoms, excited state H atoms, and ionic hydrogen (H+, H2+, H3+). The reduction ability of H2 plasma is much higher than that of temperature programmed reduction. H2 plasma can fully reduce the precursor at low temperature, avoiding the aggregation of Ni particles caused by temperature programmed reduction, resulting in smaller Ni particles size in the obtained catalyst. When the deposition-precipitation time is 10 hours, the catalytic activity of the catalyst is optimal. When the deposition-precipitation time is less than 10 hours, the content of Ni in the catalyst is relatively low, resulting in low activity. When the deposition-precipitation time exceeds 10 hours, long deposition-precipitation time may lead to an increase in the crystallinity and nickel phyllosilicate particles size. As the deposition-precipitation time increases, the deposition components gradually block the pores and reduce the specific surface area of the catalyst, resulting in a decrease in the catalytic activity of the catalyst. Under optimal preparation conditions, the conversions of CH4 and CO2 are 72.5% and 78.2%. The selectivities of H2 and CO are 86.7% and 94.2%, and H2/CO is 0.89. The energy efficiency is 4.36 mmol/kJ.-
Key words:
- CH4/CO2 reforming /
- Ni/SiO2 /
- dielectric barrier discharge plasma
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图 1 催化剂前体的（a）XRD谱图（b）FT-IR谱图
Figure 1 (a) XRD patterns and (b) FT-IR spectra of catalysts precursors
图 3 （a）Ni/SiO2-DP和Ni/SiO2-IMP的XRD谱图（b）Ni/SiO2-DP 的FT-IR谱图
Figure 3 (a) XRD patterns of Ni/SiO2-DP and Ni/SiO2-IMP (b) FT-IR spectra of Ni/SiO2-DP
图 4 （a）Ni/SiO2-DP的TEM图像（b）Ni/SiO2-IMP的TEM图像
Figure 4 (a) TEM image of Ni/SiO2-DP (b) TEM image of Ni/SiO2-IMP
图 5 Ni/SiO2-DP和Ni/SiO2-IMP的氮气吸附-脱附等温线
Figure 5 N2 adsorption-desorption isotherms of Ni/SiO2-DP and Ni/SiO2-IMP
图 6 Ni/SiO2-DP和Ni/SiO2-IMP的（a）CH4-TPD谱图（b）CO2-TPD谱图
Figure 6 (a) CH4-TPD profiles and (b) CO2-TPD profiles of Ni/SiO2-DP and Ni/SiO2-IMP
图 8 Ni/SiO2-DP和Ni/SiO2-IMP的干重整催化活性（a）反应物转化率（b）产物选择性
Figure 8 The catalytic performance of the Ni/SiO2-DP and Ni/SiO2-IMP for DRM (a) conversion of reactants(b) selectivity of products
图 9 Ni/SiO2-DP和Ni/SiO2-IMP的干重整稳定性
Figure 9 Stability test of the Ni/SiO2-DP and Ni/SiO2-IMP for DRM
图 10 （a）反应后Ni/SiO2-DP和Ni/SiO2-IMP的XRD谱图（b）反应后Ni/SiO2-DP和Ni/SiO2-IMP的TG曲线（c）反应后Ni/SiO2-DP和Ni/SiO2-IMP的拉曼光谱（d）反应后Ni/SiO2-DP的TEM图像
Figure 10 (a) XRD patterns of the Ni/SiO2-DP and Ni/SiO2-IMP after reaction (b) TG curves of the Ni/SiO2-DP and Ni/SiO2-IMP after reaction (c) Raman spectra of the Ni/SiO2-DP and Ni/SiO2-IMP after reaction (d) TEM image of Ni/SiO2-DP after reaction
图 11 TPR温度对干重整催化活性影响（a）反应物转化率（b）产物选择性
Figure 11 Effect of TPR temperature on the catalytic performance of Ni/SiO2-DP for DRM (a) conversion of reactants (b) selectivity of products
图 12 还原方法对干重整催化活性影响（a）反应物转化率（b）产物选择性
Figure 12 Effect of reduction way on the catalytic performance of Ni/SiO2-DP for DRM (a) conversion of reactants (b) selectivity of products
图 13 Ni/SiO2-DP-PR和Ni/SiO2-DP-TPR500的XRD谱图
Figure 13 XRD patterns of Ni/SiO2-DP-PR and Ni/SiO2-DP-TPR500
图 14 H2 等离子体还原时间对干重整催化活性影响（a）反应物转化率（b）产物选择性
Figure 14 Effect of H2 plasma reduction time on the catalytic performance of Ni/SiO2-DP-PR for DRM (a) conversion of reactants (b) selectivity of products
图 15 不同H2等离子体还原时间的Ni/SiO2-DP-PR的XRD谱图
Figure 15 XRD patterns of Ni/SiO2-DP-PR under different H2 plasma reduction time
图 16 沉积沉淀时间对Ni/SiO2-DP-PR干重整催化活性影响（a）反应物转化率（b）产物选择性
Figure 16 Effect of DP time on the catalytic performance of Ni/SiO2-DP -PR for DRM (a) conversion of reactants (b) selectivity of products
表 1 不同沉积沉淀时间的Ni/SiO2-DP的物理结构特征参数
Table 1 Physical structural charateristics of Ni/SiO2-DP with different DP time
Catalyst SBET/(m2·g−1) v/(cm3·g−1) d/nm Ni/SiO2-DP-4 h 247.7 0.64 8.86 Ni/SiO2-DP-10 h 242.0 0.66 9.11 Ni/SiO2-DP-16 h 223.5 0.68 9.78 
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表 2 Ni/SiO2-DP协同DBD等离子体催化干重整性能
Table 2 The catalytic performance of Ni/SiO2-DP for DRM with DBD plasma
Input power/W Conversion/% Selectivity/% CH4 CO2 H2 CO 19 25.3 23.2 60.1 68.3 21 34.6 37.8 71.6 85.1 23 45.3 51.4 77.5 89.6 25 54.1 62.6 80.1 92.1 27 72.5 78.2 86.7 94.2
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表 3 Ni/SiO2-DP热法催化干重整性能
Table 3 The catalytic performance of Ni/SiO2-DP for DRM with thermal catalysis
Reaction temp./℃ Conversion/% Selectivity/% CH4 CO2 H2 CO 600 50.6 54.8 76.9 93.9 650 67.3 72.8 81.2 96.1 700 81.1 84.5 83.6 97.6 750 89.9 91.0 84.7 98.7 800 95.0 94.2 86.1 99.1
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